Energetics and Structures of the Carbonyl Chloride Radical, Oxalyl Chloride, and Their Cations
Energetics and Structures of the Carbonyl Chloride Radical, Oxalyl Chloride, and Their Cations
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DOI：
10.1021/jp992123f
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发表时间：
1999-09
影响因子：
2.9
通讯作者：
S. Chien;K. Lau;Wai-Kee Li;C. Ng
中科院分区：
文献类型：
--
作者：
S. Chien;K. Lau;Wai-Kee Li;C. Ng
使用 Gaussian-2 (G2) 和 Gaussian-3 (G3) 理论模型对碳酰氯自由基及其二聚体草酰氯及其阳离子的结构和能量学进行了从头算研究。获得的结构结果包括 ClCO、ClCO+、(ClCO)2 的反式、顺式和左构象异构体以及连接反式和左式构象异构体和 (ClCO)2+ 的过渡结构 (TS) 的优化几何形状。报告的能量结果包括 ClCO、各种 (ClCO)2 构象异构体和过渡结构、ClCO+ 和 (ClCO)2+ 的形成热，以及 ClCO 和 (ClCO)2 的绝热和垂直电离能。获得的 G3 结果与现有的实验数据非常吻合。在某些情况下，实验数据不可用或不精确，G3 结果应该是可靠的估计。在文献中发现的三个 ClCO 实验 ΔHof298 值中，最近报道的一个 (−21.8 ± 2.5 kJ mol-1) 具有最好的农业...
An ab initio study on the structures and energetics of the carbonyl chloride radical and its dimer, oxalyl chloride, along with their cations, was carried out using the Gaussian-2 (G2) and Gaussian-3 (G3) models of theory. The structural results obtained include optimized geometries of ClCO, ClCO+, the anti, syn, and gauche conformers of (ClCO)2 and the transition structure (TS) connecting the anti and gauche conformers, and (ClCO)2+. The energetic results reported include the heats of formation for ClCO, various (ClCO)2 conformers and transition structures, ClCO+, and (ClCO)2+, as well as the adiabatic and vertical ionization energies of ClCO and (ClCO)2. The G3 results obtained are in very good agreement with the available experimental data. In some cases, where the experimental data are unavailable or imprecise, the G3 results should be reliable estimates. Among the three experimental ΔHof298 values for ClCO found in the literature, the one most recently reported (−21.8 ± 2.5 kJ mol-1) has the best agr...